Process for coating pigments with titanium hydrate



" i ze Aim United States Patent N 0 Drawing.

The present invention relates to the preparation of novel pigment coating materials and to improved methods of depositing said coating materials on various surfaces. More particularly, the present invention is concerned with the preparation of pigment coating materials having a basis of a metal alkyl alcoholate, and to improved methods of depositing said alcoholate coating materials on the unit or units comprising a solids system, i.e. an aggregate of micro particles in the commercially dry form.

It is common knowledge that there have long existed inadequacies in the properties of both pigments and vehicles leading to deficiencies in the rheological characteristics of their dispersions to be hereinafter described.

This has hampered to a considerable extent the attainment of the desired dispersion results. While the difiiculties experienced may be ascribed to both vehicle and pigment most of the research effort to date has been on the vehicle in an effort to improve its pigment wettability. This is unfortunate since pigments are equally if not more important in the overall picture.

To remedy this situation with respect to the pigment, it has become the practice to use surface-active agents and/0r pigment coatings to achieve the desirable rheological properties, particularly fluidity and cohesiveness. Nevertheless, as is commonly known, the results obtained have been indiiferent and uncertain. The reasons for this failure will now be discussed.

Surface-active agents are molecularly soluble or colloidally dispersible substances which are cationic, anionic, or non-ionic depending on their polarity, and separately co-lloidally active depending on the presence of non-polar London dispersion forces. The ability of surface-active agents to alter the rheological properties of dispersions depends on (1) their individual capacities to be adsorbed in small amounts, onto the pigment surfaces or specific sites thereof, (2) the ability of such adsorbed surfaceactive agents to be also attracted to the vehicle, and thus to act as a cohesive bond between the pigment and vehicle, and (3) the ability of such vehicle-pigment physical adducts to exert repulsion forces against each other in order to achieve dispersion fluidity. Because of the variety used of pigments and vehicles, as well as mixtures thereof, it is understandable that great difficulty is experienced in finding surface-active agents which will function adequately to fulfill the above three requirements.

In addition to the surface active agents, pigment coatings have also been resorted to. Here the aim is to envelope or encase the pigment with a much larger amount of a substance than would be possible using surfaceactive agents.

One common method of pigment coating is that performed by the pigment manufacturer on the aqueous suspensionof the pigment after completion of its preparation, but before filtration. Obviously, for the pigment coating to disperse in the aqueous suspension, said coating must, at least in the initial stage, he water-soluble. As an example, in the widely used rosination process an aqueous solution of sodium rosinate is added to and dis solved in the aqueous pigment suspension. As a result part of the sodium rosinate is adsorbed onto the pigment particles, the excess remaining in solution. Both the 3,fl25,173 Patented Mar. 13, 1962 "ice adsorbed and excess sodium rosinate are converted either into rosin by acidification or into barium or calcium rosinate by the addition of an aqueous solution of barium or calcium chloride. The rosinated coating on the pigment promotes finer pigment particle size. However, being organic, said coating forms weak Van der Waals attraction forces which subsequently tend to produce thixotropy and/or poor fluidity in the dispersion. The excess converted sodium rosinate remains moreover with the pigment as an extender and serves no specific surfactant purpose. The amount of such rosination which includes both the adsorbed and unadsorbed portions varies from 5 to 35% based on the weight of the pigment, which is a high percentage compared to the normal 0.1% tol% used of surface-active agents.

Notwithstanding the fact that the major part of the rosin or metal rosinate is present in the rosinated pigment as an extender, this does not detract from the tinctorial strength of the pigment because of the resulting finer particle size and hence the overall higher tinotorial strength of the rosinated pigment itself. On the whole, however, rosination results in an undesirable increase in the oil absorption of the pigment with a concomitant decrease in the fluidity of the resulting pigment-vehicle dispersion, such decreased fluidity being a defect particularly with respect to printing inks, since it interferes with good press distribution at high pigment loadings.

The dispersion of pigment mixtures constitutes a special case involving poor rheological properties which are even worse than those for single pigments. Through the years this has remained a major defect in paints and lacquers, as well as in thin ink systems such as those for gravure and flexographic printing. Because of the variety of pigments used in such mixtures, i.e. organic, inorganic, and metallo-organic, it is obvious that the surfaces involved constitute a wide range of Van der Waals and ionic lattice forces with the consequence that said surfaces adsorb or are wetted by the dispersion vehicle in varying degrees and in varying manner. This non-uniformity carries through even in the presence of surfaceactive agents since such agents themselves have difierent effects on different pigments and vehicles. This likewise is true where pigment coatings have been used, such as the rosination coating described above. These variable pigment surface characteristics exhibit themselves as a separation or flotation of one of the pigment components. In the case for example of greens made of a mixture of blue and yellow pigments, this generally results in the surface flotation of the yellow pigment. the case of tints in which titanium dioxide is used as the white component, the phenomenon exhibits itself as a white flotation. While flotation is not a major problem in the case of conventional heavy bodied printing inks it may on occasion exhibit itself even in these heavier ink systems. Frequently the use of silicones is of some help in the.control of flotation, but such aid as they aiford is uncertain and cannot be relied on.

This sums up the prior art, in its general aspects, of pigment dispersions, particularly of the non-aqueous types, with respect to their rheological and certain of their color characteristics. What progress has been made through the years has been empirical relating to specific instances and not the result of a generalized approach to the problem. While the aforesaid use of surface-active agents and/or coatings has been directed to both organic and inorganic pigments the dominant need has been and still is in the field of organic pigment dispersion.

In this connection it is interesting to note that while the generally better rheological properties of inorganic pigment dispersions is attributed to their higher density and larger particle size, and hence to their lower specific surface areas and lower vehicle demands, this is not the only nor indeed the prime factor involved, as will now be discussed.

It has long been known that certain high density inorganic pigments such as, for example, titanium dioxide, lead oxide, lead chromate, and lead carbonate, when dispersed in oleo and/or oleo resinous vehicles, even at high pigment concentrations, to compensate for their high densities, possess excellent fluidity even in the absence of surface-agents or coatings, in contrast to the poor fluidity of most organic pigment dispersions even in the presence of surface-active agents. Metallo-organic pigments, such as for example lead rosinate and calcium lithol red occupy a position in between the organic and inorganic types, indicating that the metal atom is in some respects of basic importance in the attainment of the rheological property of fluidity. Such increased fluidity is not, however, true of all metal atoms. For example, alumina hydrate in oleo and/or oleo resinous vehicles gives dispersions which are relatively short. Because of the fact that many inorganic pigments do possess high fluidity dispersion characteristics, they are frequently used in paint and printing ink formulations as co-pigments to improve the poor fluidity of the organic pigments present. It is of course obvious that the use of inorganic pigments for this purpose can only be done if they do not interfere with either the transparency or color requirements of the dispersion.

Notwithstanding the above fluidity advantage of many of the inorganic pigments in their dispersions, the important rheological property of high cohesiveness of dispersions of these pigments varies from excellent in the case of alumina hydrate to poor in the case of the iron oxides. Organic as well as metallo-organic pigments likewise vary with respect to good cohesiveness. Cohesiveness in dispersions relates to the attraction and bonding between the pigment and the vehicle. In a sense it would appear that cohesiveness is the opposite of fluidity, but this is not, necessarily the case, since the pigment may be thoroughly wetted and possess good cohesiveness, and at the same time the resulting pigment-vehicle adducts acting as units may repel one another, leading to good fluidity.

Since part of the instant invention is basically concerned with the attainment of desirable rheological properties in pigment dispersions, it is believed to be desirable to list these properties in order to show where the prior art fails and where the teaching of the instant invention leads to valuable results.

These desirable dispersion rheological properties are (1) good pigment wetting by the vehicle or the thermoplastic continuum, (2) eflective diminution of pigment particle size during the milling or other dispersion methods performed on the pigment vehicle mix or on the pigment-thermoplastic continuum mix, (3) high cohesiveness or internal bonding strength between the pigment and the vehicle or the thermoplastic continuum, (4) high fluidity of the dispersion where the system is of the vehicle type, (5) uniformity of the aforestated dispersion rheological properties where the pigment consists of a number of components, and (6) stabilization of the rheological properties of the dispersion against emulsification, through control of the water sensitivity of the pigment and/ or the vehicle component.

While a partial answer to the above listed rheological requirements has been achieved empirically through the years for a limited number of pigments, the direct technological attainment of these rheological attributes has not been achieved. The application of the prior art requires the trial and error examination of a large number of the surface-active agents and/or the coatings heretofore used, and there is no assurance after the completion of such extensive and time consuming examination that even a partial answer to the problem will result.

It is an important object of this invention to teach how substantially all of the above listed rheological properties may be achieved in a manner which is independent of the pigment or pigment mixture to which it is applied, and substantially independent of the vehicle or thermoplastic continuum in which the pigment is dispersed.

Thus, the instant invention consists of two basic parts, (1) new and novel pigment coating or coatings and (2) new and novel methods of applying said coating or coatings.

As a result of experimental work, it was discovered that certain metal hydrates, in particular those of the metal elements of the 4th periodic table group, subdivision A, consisting of titanium, zirconium, thallium and cerium, or combinations thereof, give properties, when applied as coatings to single pigments or mixtures thereof, which result in the attainment of marked improvement in the rheology of dispersions of said pigments, as well as in the attainment of other desirable pigmentary and dispersion properties.

Such metal hydrates, and in particular titanium hydrate, which when dispersed by themselves in many vehicles, possess in thin films, a high degree of transparency and colorlessness. When these metal hydrates are used as pigment coatings they do not therefore interfere with the color characteristics of the pigment or pigment mixture, except to diminish their 'bronziness which in itself is very desirable.

In the ease of titanium hydrate, this pigment when dispensed in an oleo or oleoresinous vehicle, possesses a degree of transparency which is substantially equal to that of alumina hydrate which is regarded as the standard in this property. This is in contrast to the high opacity of titanium dioxide, which is the dehydrated and calcined form.

It was further discovered that the metal hydrates of the stated group adhere tenaciously to various surfaces, and are therefore suitable for use as coatings. These surfaces include pigment surfaces, which is the specific area of the invention now being discussed, but are not limited thereto, as will be discussed below.

With respect to the greatly enhanced water resistance of metal hydrate coated pigments, and in particular to titanium hydrate coated pigments, that such pigments are of marked potential value in the making of lithographic printing inks. When lithographic inks are made using ordinary or untreated pigments, such inks, because of their relatively poor water resistance, emulsify water or aqueous fountain etch during the press operation. Such emulsification interferes with the eflicient operation of the press and results in poor printability. The use of metal hydrate coated pigmented inks, on the other hand, possessing a high degree of water resistance, holds emulsification to very low limits and permits the attainment of improved printability.

In addition to the above stated benefit deriving from increased water resistance of metal hydrate coated pigments, such benefit may also be imparted by a similar treatment to markedly hydrophilic particle-like substances, such as, for example, starch and starch derivatives. The metal hydrate coating of such hydrophilic substances, and the attainment of a high degree of water resistance thereby, is of great potential value in post-treatment of uncoated and coated printing papers, as well as of paper products in general containing starch. It is of potential value also in other industrial fields, such as the textile, ceramic, and leather, where improved and/0r controlled water resistance has long been sought.

The second part of the invention has to do with the methods discovered for selectively and specifically coating pigments and other surfaces in situ with a suitable metal hydrate of the group hereinbefore mentioned. In the one application phase, the metal hydrate is deposited at the time of its formation, in situ, onto the pigment or other surface, said formation or deposition taking place in the absence of the other dispersion components such as vehicle or thermoplastic continuum.

In the case where the substance being coated is a pig- All I 1 ment, said pigment being in the commercially dry and pulverized form, the pigment is first suspended in a substantially non-polar medium by means of active stirring. Any suitable non-polar medium may be employed such as aliphatic and aromatic hydrocarbons, examples of which are:

ALIPHATIC HYDROCARB ONS Boiling range, F.

It is preferred, however, to employ hexane as the nonpolar suspending medium as it evaporates at a fast rate, and the instant invention will hereinafter be described in connection with its use unless otherwise stated.

To the suspension of the pigment in hexane there is added during active stirring a hexane solution of a metal alkyl alcoholate in which the metal belongs to the aforementioned group of the periodic table and the alkyl alcohol group of which belongs to the saturated alcohols with a carbon chain length of from C to C It is preferred, however, to employ tetrabutyl titanate. Simultaneous formation and deposition of the metal hydrate takes place in situ, as a coating onto the pigment surface, as a consequence of the complete hydrolysis of the metal alkyl alcoholate to the tetra hydrate.

More specifically, according to this invention, the formation and deposition of said coatings can occur simultaneously as a single stage process, or as a two stage process with formation and deposition taking place separately.

The formation of said coatings is the consequence of a chemical reaction or reactions.

In one formation method, one of the two reactants resides wholly on and in the solids system, whereas the second reactant is uniformly distributed in dilute form in a medium in which the solids system is placed, said medium being in the gaseous, liquid, or thermoplastic state. The reaction between the two reactants takes place at the medium-solids interface, with the reaction product or coating being deposited wholly on and in the surface of the solids system.

The reaction goes to completion quickly since one of the two reaction products, namely the coating itself, is substantially insoluble, or non-volatile, in the medium, and further since the second reaction product is either soluble, or volatile, in the medium and is diluted by the medium as it is formed and thus substantially removed from the reaction site. When the reaction is completed the coated solids system is removed from the medium. This in situ formation and deposition of a coating constitutes one part of this invention.

An example of this reaction method, although the invention is not limited thereto, is the case where the first reactant is moisture residing on and in the solids system, the second reactant is a metal alkyl alcoholate, preferably tetrabutyl titanate having the formula the solids system a commercially dry and pulverized pigment, and the medium, hexane, a fast evaporating liquid. In this case the first reactant, water, is substantially insoluble in the hexane medium, which localizes the reaction site to the pigment. Furthermore, the tetrabutyl titanate reactant is soluble in the hexane medium, which provides a well defined reaction interface. The first reaction product is titanium hydrate which is insoluble in the hexane medium, and the second reaction product is butyl alcohol which is soluble in and diluted by the hexane medium as soon as it is formed and hence is rendered substantially incapable of reversibly reacting with the deposited titanium hydrate.

In part, this invention has to do with the above disclosure of the conditions of the reaction by means of which said reaction leading to the formation of titanium tetrahydrate proceeds to completion. This constitutes an advance over the prior art, which prior art (see R. Sidlow, Recent Developments in Organic Derivatives of Titanium, Jour. Oil and Colour Chemists Assoc., vol. 4-1, No. 8, pp. 577-586, 1958), states that the hydrolysis of tetrabutyl titanate does not proceed to completion, but rather that after a single butyl group has been hydrolyzed, two molecules of such tributyl titanium mono hydrate condense to form a molecule of dititanium hexa butylate with the regeneration of a molecule of Water.

Control experiments which were made explicitly show that when stoichiometric proportions of water and tetrabutyl titanate are reacted under the above disclosed conditions, the reaction product is titanium tetrahydrate which is obtained in dry pigmentary form and in the correct stoichiometric amount. It is obviously most unlikely that Sidlows di-titanium hexabutylate would be a dry pigment, because of its contained six butyl groups which would tend to give the above condensation product liquid characteristics. Furthermore, the stoichiometric amount of the di-titanium hexabutylate condensation product produced would be approximately three times greater than for the titanium tetra hydrate, and hence would not conform to the experimental results obtained by the disclosed process.

The water required for the hydrolysis may be, and generally is, adequately furnished by the residual moisture contained in and on the pigment particles themselves, such moisture being present in the range of 0.5% to 2.0% by weight. The amount of water in this range is sufiicient to hydrolyze the quantity of the metal alkyl alcoholate used which may be in the range of 0.5% to 10.0%.

In certain cases, however, as that of the fluorescent pigments, which are glass-like, the percentage of. water necessary for optimum coating results may be as high as 12% based on the weight of the pigment. The conditions for the coating of these fluorescent pigments differ from those for ordinary pigments, and these conditions will be described below in the section dealing with them.

With respect to the metal alkyl alcoholates which may be used, these are restricted to the alcoholates of the metals of the 4th group subdivision A of the periodic table, as hereinbefore mentioned. The alcoholates of the 4th group subdivision B, on the other hand, cannot be used, since, tin butylate, for example, is stable to hydrolysis under the conditions of the invention. Nor can the alcoholates of the 3rd group be used since, for example, tributyl aluminate, while it hydrolyzes according to the conditions of the instant invention, its hydrolysis product aluminum hydrate not only possesses poor adhesion to surfaces but also possesses poor water resistance. This is not to say that tributyl aluminate cannot be used as a coating reactant as will later be disclosed but rather that it cannot be used as a reactant for the. making of a metal hydrate coating.

The metal alkyl alcoholates used are preferably, as indicated above, the butyl derivatives, since the lower alcoholates up to and including the propylates hydrolyze too rapidly. The alcoholates higher than the butylates, on the other hand, hydrolyze too slowly. Neither type is however excluded from the invention, nor are mixtures of them excluded. While the saturated alcoholates are preferred, the unsaturated alcoholates are likewise not excluded from the invention.

With regard to the amount of the metal alkyl alcoholate used for the metal hydrate coating of pigments,

this is dependent on the particle size and density of the pigment, or more accurately on the surface area. Generally speaking the high surface area pigments, such as for example benzidine yellow, require about tetrabutyl titanate, whereas the low surface area pigments such as, for example titanium dioxide, require only about 2%. Other pigments require intermediate quantities. Then too there is the matter of the thickness of coating required, depending on the desired results. In general, it may be said that the range of the metal alkyl alcoholate used would be from 0.1% to 20.0% on the weight of the pigment. I

The types of pigments which may be employed in accordance with the instant invention are as follows:

HIGH DENSITY PIGMENTS Titanium dioxide Antimony oxide Chrome yellow Chrome orange LOW DENSITY PIGMENTS Molybdate orange Vermillion Barium sulfate With regard to the liquid medium used, as stated the types useful in the instant invention are the aliphatic and aromatic hydrocarbons, with the aliphatic hydrocarbons preferred because of lower solubility for certain pigments as well as their lower cost. Optimum results are obtained by the use of hexane because of its fast evaporation rate. While the polar type liquids such as the alcohols, esters, and ketones are considered less suitable because of the possibility of their reacting with the metal alkyl alcoholate, their use is considered Within the scope of the invention when used as medium components along with the hydrocarbons.

Another method of depositing a metal hydrate reaction product in situ as a coating onto a solids system, in accordance with this invention, is subjecting the commercially dry and pulverized pigment or other surface to vapors of the metal alkyl alcoholate, said system being contained in a closed rotating chamber which tumbles the pigment and thus ensures substantially uniform reaction of the metal alkyl alcoholate with the adsorbed moisture on the pigment or other surfaces.

The invention will be described in greater detail in the following examples which are set forth for the purpose of illustration and no specific detail contained therein should be construed as being limitative.

Example I 100 parts by weight of any high density type of pig ment, such as chrome yellow or titanium dioxide and 100 parts by weight of hexane are stirred mechanically for 5 minutes whereby a smooth suspension is obtained. To this suspension is added at room temperature, with stirring, a solution of 1.7 parts by weight of tetrabutyl titanate in 3.0 parts by weight of hexane, whereby the pigment suspension is made markedly more fluid. After completion of the addition of the above tetrabutyl titanate/hexane solution, the mixture is stirred for 30 minutes, and then allowed to stand for 2 hours. The supernatant hexane is then drained off, the mixture filtered and the coated pigment dried. The hexane may be recovered.

Example II 30 parts by weight of. a low density pigment such as benzidine yellow and 100 parts by weight of hexane are stirred mechanically for 5 minutes whereby a smooth suspension is obtained. To this suspension is added at room temperature, with stirring, a solution of 1.7 parts by weight of tetrabutyl titanate in 3.0 parts by weight of hexane, whereby the pigment suspension is made markedly more fluid. After the addition of the above tetrabutyl tita'nate/hexane solution, the mixture is stirred for 30 minutes, and then allowed to stand for 2 hours. The

supernatant hexane is then drained off, the mixture filtered and the coated pigment dried. The hexane may be recovered.

As was pointed out above, this invention may be applied to other pigments as follows:

CARBON BLACK PIGMENTS When channel carbon blacks of low cost printing ink and rubber grades are coated with a metal hydrate in accordance with the disclosure, the resulting pigments when dispersed in an oleo vehicle such as for example heatbodied linseed oil (#3), said dispersion possesses superior fluidity, cohesiveness, jetness of tone and water resistance, in comparison to dispersions made using even higher priced blacks containing the conventional C O coating. This is of particular importance since C O coated blacks are made at high temperatures which burns off a substantial part of the black, and which therefore increases the cost of such blacks.

Furnace carbon blacks when similarly coated also give dispersions which possess superior fluidity, cohesiveness, jetness of tone, and water resistance in comparison to the untreated furnace black. Both channel and furnace blacks, so treated, when dispersed in rubber, give dispersions which indicate superior wettability and greater cohesiveness, these properties being of importance in the overall toughness and strength of the compounded rubber.

The herein inventive concept includes not only a method of coating carbon blacks with a substantially transparent metal hydrate but also, in the case of rubber compounded with such coated pigments, rubber products such as automobile tires, belting, foot-wear, and rain-wear, for which products improved toughness and wear resistance have long been sought.

ORGANIC PIGMENTS When lithol red, as an example of an organic pigment, which in its barium and calcium forms is widely used in the printing ink and paint fields, is not similarly coated in the aforementioned manners, dispersions made from these pigments for use in printing inks are limited, more or less, to the conventional letterpress and gravure printing processes, since flexographic and lithographic inks made from these pigments suffer from water sensitivity which leads to emulsification and subsequent deterioration of the ink system. Lithol reds which have however been coated with a suitable metal hydrate overcome this difiiculty.

The benefits accruing from the surface treatment of the lithol reds are merely one example of the effectiveness of such treatment in the organic colored pigments. It should be noted, however, that said benefits are dependent on the extent to which the coating reaction product is deposited on the individual unit pigment particles, rather than on the coarser pigment agglomerates, since if these agglomerates are broken up only on subsequent dispersion, many of the unit particles will be only partially coated. This situation is due to the fact that the Van der Waals secondary valence forces which are predominately present in organic molecules, as forces of attraction, are more difiicult to disrupt than the weaker forces of ionic lattice attraction present in inorganic pigments. An answer to this problem involved in the coating of organic pigments, will be presented later in the section on flushed" color bases and the flushing process.

Before leaving the organic pigments comment will be made on a special type, namely the fluorescent pigments which were previously referred to. Because of the functional importance of these daylight fluorescent pigments. they will be treated specially.

Q FLUORESCENT COLORED PIGMENTS In the present state of the art the daylight fluorescent pigments cannot, for all practical purposes, be used except with diificulty in the making of inks for printing by the letterpress, lithographic, gravure, or fiexographic processes, because of the poor fluidity and cohesiveness of their vehicle dispersions. These poor rheological properties result in poor distribution of the ink on the press and consequent poor printability often requiring two impressions. It is only in the silkscreen process that fluorescent pigment inks can be used, since this process does not require press distribution. Because of this situation the graphic art industry has suffered from lack of volume printing with these otherwise highly desirable fluorescent pigmented inks.

When, however, these fluorescent pigments which are glass-like in structure, are coated according to the aforementioned disclosures with a metal hydrate, marked improvement is obtained in the rheological properties of their dispersions. Printing inks made using such treated fluorescent pigments perform satisfactorily on conventional letterpress, lithographic, gravure, and flexographic presses, and a single impression gives good commercial printing results of high tinctorial strength. Furthermore, the coated pigments in these inks settle out only to a minimum after months of standing, in contrast to the rapid settling out and hard packing which occur in dispersions of the uncoated fluorescent pigments of commerce.

In the coating of the fluorescent pigments it was further discovered that the ordinary methods previously described for metal hydrate coating, did not give entirely satisfactory results, and that it was necessary to pre-treat the pigment with water, while the pigment was in the form of a stirring suspension in the hexane medium, before adding the metal alkyl alcoholate to said suspension. The reason for this is that the fluorescent pigment being glass-like in its normal commercial form does not possess suflicient water to serve as a reactant, and that it is only when the water is added in the manner described can the unit pigment particles (the consequence of fine grinding and classification) be moistened and kept separate at the same time. The percentage of water based on the weight of the pigment used is generally in the range of to 12%, with 9% as the preferred amount. The range of metal alkyl alcoholate is 2 to 10%, with 5% being preferred.

INORGANIC COLORED PIGMENTS INORGANIC EXTENDER PIGMENTS In the case of hydrated clay and precipitated calcium carbonate extender pigments which are widely used, the low cost coating of these and other extenders by the metal hydrate process heretofore described markedly improves the rheological properties of dispersions of these pigments as well as their water resist-ance. This makes these extender pigments of increased usefulness in many fields particularly in the rubber compounding field for improved strength and wear resistance.

METALLIC PIGMENTS One of the useful properties of the metallic pigments such as aluminum, bronze, and copper, in the form of their dispersions, is their high degree of light reflectance. To a large extent this is due to their leafing, by means of Which the individual metal flakes tend to lie flat on, or float on, the film of the dispersion vehicle. In the aggregate such leafed particles approximate a solid or continuous reflecting surface. The property of leafing is attained by the use of 'stearic acid during the stamping operation. Stearic acid, however, because of its low polarity and low molar adhesion, causes a low degree of adhesion to exist between the metallic pigment and the vehicle, causing rub-off in the case of printing ink and flake-off and poor weathering in the case of paint.

Metallic pigments which have been coated with a metal hydrate possess in their dispersions markedly improved cohesion. However, if the amount of coating applied is too great the metallic reflectance will be impaired because of insufiicient leafing due to too marked wetting of the pigment by the vehicle. It was discovered, however, that by reducing the amount of coating to about A that normally used, namely using for a metal hydrate coating about 0.3% for example of tetrabutyl titanate, that there is obtained not only good cohesion but even improved light reflectivity.

PAPER In the case of uncoated papers, such as for example common newsprint, facial and toilet tissue, sized and calendered, glassine and bond stocks, the coating of these by either a suitable metal hydrate, in accordance with the instant invention, imparts a substantial degree of Water resistance. Such water resistant products may be used for the preparation of paper substitutes for textile wearing apparel, as well as for their use as water resistant .multi-wall shipping bags, paper fibre containers, and corrugated paper containers. Coated printing papers, particularly those used for printing by the lithographic process are rendered substantially water resistant by the aforestated metal hydrate process, and therefore are not subject to distortion by the moisture involved in this printing process.

TEXTILES In accordance with the instant invention, natural textiles such as, for example, cotton and linen, may be rendered water resistant to a substantial degree by coating with a suitable metal hydrate. With wool and silk on the other a somewhat lesser degree of water resistance is obtained. With the synthetic textiles such as, for example, nylon, rayon, and cellulose acetate, a high degree of water resistance may be achieved. In all of these textile applications the material is merely immersed in a hexane solution of the metal alkyl alcoholate, the excess squeezed out and the hexane allowed to evaporate. They constitute a quick and economical method for water resistant treatment without affecting the porosity of the material, or the drape and hand. Felts may be similarly treated.

LEATHERS NON-VITREOU S CERAMICS Non-vitreous ceramics such as bricks and concrete building blocks may be made water resistant by immersion in a hexane solution of a suitable metal alkyl alcoholate. The non-vitreous object thus becomes substantially waterproofed. Instead of using the emmersion procedure, the solution may be either brushed or sprayed on the outer or non-bonding surface leaving the bonding surface water receptive for mortar application, or the exposed brick surface after erection may be brushed or sprayed with the coating solution. Not only does this treatment result in making water resistant non-vitreous building materials, but also in substantially increasing the weatherability of such products, as well as the weatherability of the bonding mortar. Building materials such as for example gypsum wall boards and wood may likewise be waterproofed.

NEWSPAPER INKS The instant invention is particularly advantageous in the preparation of newspaper printing inks which are substantially made by dispersing the pigment, black or colored, in a mineral or petroleum oil vehicle.

Newspaper inks dry by penetration of the ink and/or its contained vehicle into the relatively porous paper stock. If the printing, however, is done at high speeds, as in the case of the Sunday editions of the large city newspapers, the ink cannot be absorbed sufliciently fast and hence offsets and collects onto the impression cylinder or cylinders. Such offsetted ink constitutes a relief printing design, which when the reverse side of the sheet or web is printed, is imposed on the printing of said reverse side, through the added pressure transferring more ink from the printing plate. This printing defect, known as 2nd impression offset, is particularly objectionable to advertisers. gree be corrected by lowering the viscosity of the ink which increases its rate of penetration. However, when this is done, there is the likelihood that the increased penetration will cause excessive show-through or shadowing and in extreme cases even strike-through which is the through-penetration of the vehicle. The prior practice in the art of newspaper inks, therefore, is the adjustment of the ink viscosity to hold 2nd impression offset and show through at a minimum. This is extremely diflrcult to do, with the consequence that both of the above defects are still largely present in high speed newspaper printing.

After considerable experimentation, I discovered that both of the above printing defects can be eliminated by increasing the initial penetration of the ink and simultaneously retarding its subsequent penetration. This represents a marked advance in the art of newspaper ink formulation and printing. These phenomenal results were achieved by the addition to the newspaper ink of from 0.25 to 5% of a metal alkyl alcoholate of the instant invention, preferably tetrabutyl titanate, which addition results in the coating of the contained pigment by the metal hydrate, the mineral oil vehicle functioning as the non-polar medium.

The following examples may be cited, as representative of the new and improved newspaper inks:

2nd impression offset can to a certain de- 12 BLACK NEW-S INK Percent Carbon black 12.0 Mineral oil 86.0 Disperse and add tetrabutyl titanate 2.0

COLORED NEWS INK Lithol red barium 10.0 Mineral oil 88.0 Disperse and add tetrabutyl titanate 2.0

I claim:

1. A process for coating pigments which comprises applying to a granular pigment containing from 0.5% to 2.0% of moisture on the dry weight of the pigment and suspended in a non-polar medium selected from the group consisting of hexane and octane a titanium alkyl alcoholate in the proportion of .3 to 1.7 parts of said alcoholate for 30 to parts of said pigment, said alkyl radical containing from 3 to 10 carbon atoms in solution in said non-polar medium under conditions to deposit solely on the surface of said granular pigment a titanium hydrate and separating the coated pigment from said medium.

2. The method of preparing an ink which comprises applying to a granular pigment containing from 0.5% to 2.0% of moisture on the dry weight of the pigment and suspended in a non-polar medium selected from the group consisting of hexane and octane a titanium alkyl alcholate in the proportion of from .3 to 1.7 parts of said alcoholate for 30 parts to 100 parts of said pigment, said alkyl radical containing fro-m 3 to 10 carbon atoms in solution in said non-polar medium under conditions to deposit solely on the surface of said granular pigment a titanium hydrate, separating the coated pigment from said medium and thereafter incorporating said coated pigment in an ink vehicle.

References Cited in the file of this patent UNITED STATES PATENTS Blumenfield et a1. Jan. 7, 1936 Haslam June 21, 1960 OTHER REFERENCES 

1. A PROCESS FOR COATING PIGMENTS WHICH COMPRISES APPLYING TO A GRANULAR PIGMENT CONTAINING FROM 0.5% TO 2.0% OF MOISTURE ON THE DRY WEIGHT OF THE PIGMENT AND SUSPENDED IN A NON-POLAR MEDIUM SELECTED FROM THE GROUP CONSISTING OF HEXANE AND OCTANE A TITANIUM ALKYL ALCOHOLATE IN THE PROPORTION OF .3 TO 1.7 PARTS OF SAID ALCOHOLATE FOR 30 TO 100 PARTS OF SDAID PIGMENT SAID ALKYL RADICAAL CONTAINING FROM 3 TO 10 CARBON ATOMS IN SOLUTION IN SAID NON-POLAR MEDIUM UNDER CONDITIONS TO DEPOSIT SOLELY ON THE SURFACE OF SAID GRANULAR PIGMENT A TITANIUM HYDRATE AND SEPARATING THE COATED PIGMENT FROM SAID MEDIUM. 